Early detection of exposure to a toxic chemical, e.g., in a military context, can be life-saving. We propose to use machine learning techniques and multiple continuously measured physiological signals to detect exposure, and to identify the chemical agent. Such detection and identification could be used to alert individuals to take appropriate medical counter measures in time. As a first step, we evaluated whether exposure to an opioid (fentanyl) or a nerve agent (VX) could be detected in freely moving guinea pigs using features from respiration, electrocardiography (ECG) and electroencephalography (EEG), where machine learning models were trained and tested on different sets (across subject classification). Results showed this to be possible with close to perfect accuracy, where respiratory features were most relevant. Exposure detection accuracy rose steeply to over 95% correct during the first five minutes after exposure. Additional models were trained to correctly classify an exposed state as being induced either by fentanyl or VX. This was possible with an accuracy of almost 95%, where EEG features proved to be most relevant. Exposure detection models that were trained on subsets of animals generalized to subsets of animals that were exposed to other dosages of different chemicals. While future work is required to validate the principle in other species and to assess the robustness of the approach under different, realistic circumstances, our results indicate that utilizing different continuously measured physiological signals for early detection and identification of toxic agents is promising.